Charge Density Analysis of the (C—C)→Ti Agostic Interactions in a Titanacyclobutane Complex.
The experimental electron density study of Ti(CHMe)[(CH)CMe] provides direct evidence for the presence of (C—C)→Ti agostic interactions. In accord with the model of Scherer and McGrady, the C—C bond densities no longer show cylindrical symmetry in the vicinity of the Ti atom and differ markedly from...
| Publicado en: | Journal of the American Chemical Society Vol. 131; no. 17; pp. 6154 - 6161 |
|---|---|
| Autores principales: | , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
5/6/2009
|
| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=39990867&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 39990867 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 5/6/2009 vid: 131 iid: 17 pid: 997 pub: American Chemical Society artinfo: ui: 39990867 10.1021/ja807649k ppf: 6154 ppct: 7 formats: tig: atl: Charge Density Analysis of the (C—C)→Ti Agostic Interactions in a Titanacyclobutane Complex. aug: au: Scheins, Stephan Messerschmidt, Marc Gembicky, Milan Pitak, Mateusz Volkov, Anatoliy Coppens, Philip Harvey, Benjamin G. Turpin, Gregory C. Arif, Atta M. Ernst, Richard D. affil: Department of Chemistry, University of New York at Buffalo, Buffalo, New York 14260 Department of Chemistry, Middle Tennessee State University, Mufreesboro, Tennessee 37132 Department of Chemistry, University of Utah, Salt Lake City, Utah 84112 su: Electron distribution Symmetry (Musical composition) Electron configuration Solid state physics Chemical reactions sug: subj: Electron distribution Symmetry (Musical composition) Electron configuration Solid state physics Chemical reactions ab: The experimental electron density study of Ti(CHMe)[(CH)CMe] provides direct evidence for the presence of (C—C)→Ti agostic interactions. In accord with the model of Scherer and McGrady, the C—C bond densities no longer show cylindrical symmetry in the vicinity of the Ti atom and differ markedly from those of the other C-C bonds. At the points along the C—C bond where the deviation is maximal the electron density is elongated toward the metal center. The distortion is supported by parallel theoretical calculations. A calculation on an Mo complex in which the agostic interaction is absent supports the Scherer and McGrady criterion for agostic interactions. Despite the formal d° electron configuration for this Ti(IV) species, a significant nonzero population is observed for the d orbitals, the d orbital population is largest for the d orbital, the lobes of which point toward the two Cα atoms. Of the three different basis sets for the Ti atom used in theoretical calculations with the B3LYP functional, only the 6-311 ++G** set for Ti agrees well with the experimental charge density distribution in the Ti—(C—C) plane. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2009 holdings: @attributes: islocal: N |
|---|